Method for production of cationic surfactant

ABSTRACT

New type of water-soluble, cationic surfactant having an excellent flocculating effect is obtained by subjecting a raw material aromatic hydrocarbon compound to polycondensation, chlorination, and amination reactions.

ilrtited States Patent Suzuki et a5. Sept, 9, 1975 METHOD FOR PRODUCTIONOF [58] Field at Search 260/564 E; 204/163 R CATHONIC SURFACTANT [75]Inventors: Shigeyuki Suzuki, Machida; isamu [56] References CitedKaneda; Hiroshi Endo, both of OTHER PUBLICATIONS y Kazuo y Yamato;Walker, Formaldehyde, 2nd Ed., 1953 pp. Tatiao Horiguchi; Kazumasa 33345 Yamamoto, both of Yokohama, all of Japan Assignees: Kureha KagalkuKogyo K.K.,

Tokyo; Kurita Water Industries Ltd., Osaka, both of Japan Filed: Oct.18, 1971 Appl. No.: 190,356

Foreign Application Priority Data Octv 17, 1970 Japan 45-90961 US. Cl.260/564 E; 204/163 R; 252/545; 260/288 R; 260/296 R; 260/566 F;

260/5676 M; 260/583 R; 260/584 R Int. Cl. (107i: 119/00 Noller,Chemistry of Organic Compounds, 3rd Ed., pp. ll5l 16, 259 and 497-498.

Smith, Open Chain Nitrogen (Iompounds, Vol. 1, pg. 271, (1965).

Primary ExaminerLeon Zitver Assistant Examiner-Gerald A. SchwartzAttorney, Agent, or Firm-Wenderoth, Lind & Ponack [5 7 ABSTRACT 2Claims, No Drawings METHOD FOR PRODUCTION OF CATIONIC SURFACTANT Thisinvention relates to a method for producing a water-soluble substancehaving a cationic type interfacial activity. More particularly, it isconcerned with a method for producing a new cationic surfactant, whereinaromatic hydrocarbon compound having side chains which contain thereinactive hydrogen capable of substitution by chlorine (hereinafter simplyreferred to as active hydrogen, is subjected to polycondensationreaction by using formaldehyde, then the resultant polycondensate ischlorinated under irradiation with, and is further reacted withultraviolet light various amines to connect the same to a water-solublecationic substance.

So far, it has been known to produce cationic surfactants by introducingthe chloromethyl radical into aromatic compounds such as dodecylbenzene,octylbenzene, etc.; thereafter the compound is reacted with pyridine,trialkylamine, etc., to convert it to a pyridinum salt, quarternaryammonium salt, etc. These compounds, however, have weak ability toflocculate solid particles suspended in water; hence they cannot serve apractical use.

It is therefore an object of the present invention to provide a new typeof cationic surface activating substance capable of exhibitingsufficient flocculating effect in practical use.

It is another object of the present invention to provide a method forproducing such cationic surfactant, wherein an aromatic compound havingside chains which contain therein active hydrogen is polycondensed underparticular reaction conditions to obtain a polycondensate of thearomatic compound, having a large molecular weight, then thepolycondensate is chlorinated under irradiation with ultraviolet ray tosubstitute the active hydrogen in the side chains with chlorine, whichis highly reactive, and finally this chlorinated substance is reactedwith amine derivatives such as thioureas, alkylamines, pyridines, etc.,to connect the same to a cationic surface activating substance having anexcellent flocculating effect.

The foregoing objects and details of the present invention will becomemore apparent from the following description thereof when read inconjunction with preferred examples.

First of all, the aromatic hydrocarbon compounds used herein and havingside chains which contain therein active hydrogen capable of beingsubstituted by chlorine are designated as follows.

a. benzene derivatives having the methyl group such as toluene, xylene,mesitylene, etc.;

b. alkylbenzene containing more than one alkyl group such asethylbenzene, dibutylbenzene, etc.;

c. alkylnaphthalene containing more than one alkyl group, represented bythe methyl group, as above;

Important in the present invention is that the abovementioned aromaticcompound as the starting material should be subjected topolycondensation in the first step so as to connect it to an aromaticcompound having large molecular weight which is then further subjectedto chlorination and subsequent amine treatment to connect the same to ahigh molecular, water-soluble, cationic substance. Mere chlorination andamine treatment of the aromatic compound does not result in the cationicsubstance having required flocculating effect.

In this first step of polycondensation, any of the raw materialcompounds as classified hereinabove is caused to react with an aqueoussolution of formalin, para-for maldehyde, or trioxane in the presence ofa catalyst such as mineral acids (e.g., sulfuric acid, perchloric acid),organic sulfonic acid (e.g., benzene sulfonic acid, paratoluene sulfonicacid, etc.), or Lewis acids (e.g., zinc chloride, aluminum chloride,etc.)

Solvents such as organic acids (e.g., acetic acid, propionic acid,etc.), organic chlorides (e.g., chloroform, carbon tetrachloride,1,2-dichlor0ethane, perchloroethylene, etc.), or others may be used toenable the reaction to proceed smoothly. Nitrobenzene, benzonitrile,etc., may also be used as the solvent. These solvents are properlyselected in an attempt to facilitate the polycondensation reaction andto conduct the manufacturing process in a most advantageous manner. Forexample, when the polycondensation is to be conducted betweenmeta-xylene as the raw material and pformaldehyde in the presence ofsulfuric acid as the catalyst, if acetic acid is used as the solvent, ahigh molecular polycondensate can be obtained at a higher rate of yieldthan in the case of using no acetic acid. Also, if the reaction isconducted by using a solvent such as l,2dichloroethane at the boilingpoint thereof, it is possible to remove water produced by thepolycondensation reaction as the azeotropic substance, hence thereaction proceeds quickly. A solvent such as 1,2- dichloroethane is alsosuited as the solvent for chlorination in the subsequent step.

The polycondensate thus obtained should have a mean molecular weight of200 and above to give the end product a desired capability offlocculation. The upper limit of the mean molecular weight is difficultto determine. Any value which is capable of yielding a water-solublecationic surfactant as the end product will meet the present purpose. Ingeneral, the polycondensate should have a mean molecular weight range offrom 200 to 3,000.

In the second step of chlorination reaction, the polycondensate isdissolved in a solvent and the reaction is conducted under suchconditions that chlorine may be selectively substituted for the activehydrogen present in the side chains of the aromatic compound withoutcausing substitution for hydrogen in the aromatic nucleus (aromaticsubstitution). This reaction is conducted, for example, by blowingchlorine gas into the reaction vessel from the bottom part thereof underultraviolet ray irradiation, while refluxing the solvent. The solventfor this purpose is: dichloromethane, chloroform, carbon tetrachloride,1,2-dichloroethane, perchloroethylene, chlorobenzene, benzene,nitrobenzene, benzonitrile, etc. The chlorination should prefer ably beconducted to the extent that one chlorine atom is introduced into mostof the side chains.

The polycondensate material thus chlorinated is then brought to thethird step reaction, where it is reacted with amines such as thioureas,etc. For this reaction,

3 the following method is adopted, for example: (1 one or more kinds ofbases, particularly amine derivatives are directly added to thechlorination reaction mixture and are reacted with each other; or (2)the polycon- 4 ter the precipitated substance was removed by filtrationunder pressure. As the result, 25.37 kg. of 1,2- dichloroethane solutioncontaining therein 3.76 kg. of meta-xylene condensate was obtained. Themelting densed material is dissolved in a solvent such as, for in- 5point of the m-xylene condensate dissolved in this solustance,tetrahydrofuran, 1,2-dichloroethane, perchlotion was approximately 290Cand its mean molecular roethylene, acetone, methanol, or water in anamount weight was 1,630. of 1 to 20 percent with respect to the totalsolvent, and Into this 1,2-dichloroethane solution of the aboveis thenreacted with the amines. mentioned m-xylene condensate, chlorine gas wasThe useful amine derivatives in this treatment are: blown at a rate of10 l/min by reflux under irradiation thioureas such as thiourea, alkylthiourea, phenyl thio of high voltage mercury lamp so as to chlorinatethe sourea, etcs, pyridines such as pyridine, picoline, quinolution andto extract 1,2-dichloroethane therefrom. line, etc.; trialkyl aminessuch as dimethyl benzylamine, 5.78 kg. of chlorinated substance of lightbrown color dimethyl laurylamine, etc.; dialkyl amines such as diwasobtained, the chlorine content of which was found ethyl amine, diethanolamine, etc.; monoalkyl amines to be 34.8 percent. such as ethyl amine,ethanol amine, etc.; and Schiff 100 g. of this chlorinated substance wasdissolved in bases such as benzylidene aniline. 500 g. of acetone, towhich 73 g. of thiourea was added, The extent of amination of thechlorinated polyconand the batch was agitated for 2 hours under reflux.densate is preferably such that the chlorine which was Upon filtrationand drying of the reacted substance, introduced into the material at thepreceding step is to- 173 g. of a solid substance of light yellow colorwas obtally reacted with the amines. In practice, however, if tained. Asthe results of measurement by infrared ray the degree of reaction israised to such an extent that spectrum analysis, elementary analysis,etc., this solid the material is rendered water-soluble, sufficientflocsubstance was recognized to be the intended isothiculating effectcan be imparted to the end product. uronium salt. (This substance willhereinafter be re- The thus produced water-soluble cationic salts ofisoferred to as A.) thiuronium type, pyridinum type, and quarternary am-179 g. of pyridinium salt was obtained by the same monium type, etc.,are quite novel substances which process as described in the foregoingexcept that 100 g. cannot be found in any technical literatures so farpubof pyridine was used in place of 100 g. of thiourea. lished. (Thissubstance will hereinafter be referred to as B.) The water-solublecationic surfactant according to By using these two substances A and B,tests for their the present invention is in general a solid substance offlocculating effect was conducted with respect to kaolight yellow orlight brown, color is soluble in water and lin suspension and an aqueoussolution of an acidic dye methanol, an is very useful for a variety ofpurposes (Amaranth red), the results of which are as follows. such asflocculation of organic and inorganic particles a. Test in kaolinsuspension: suspended in water, flocculation of anionic organicSuspension liquid prepared by dispersing 5g of kaolin substancedissolved in water, and other uses. in 100 cc of water was poured inglass cylinders of 30 In order to enable skilled persons in the art toreduce cm in depth. To this kaolin suspension in each cylinder, theinvention to practice, the following preferred examthe above-mentionedsubstances A and B were added ples are presented. It should, however, benoted that respectively so that the content of each of these subtheinvention is not limited to these examples alone, but stances may be0.01 percent with respect to the total any changes and modifications maybe made within the quantity of water. Besides tthis, two othersubstances purview of the invention as afforded by the appended forcomparison purposes were added to the same quanclaims. tity of thesuspension liquid at the same content as in the substances A and B. Thestates of flocculation and EXAMPLE 1 precipitation were compared amongthese samples. Into a three-necked flask of a 30-liter capacity, thereThe following Table 1 shows the results of the compariwere charged 3.0kg. of meta-xylene, 1.27 kg. of parason, from which it is recognizedthat the cationic surformaldehyde, 0.3 kg. of 98 percent conc. sulfuricacid, factant obtained by the present invention has higher and 9.0 kg.of acetic acid. The batch was subjected to speed of precipitation at theinterface of the supernant reaction for 5 hours at a temperature of from1 10 to liquid and the kaolin suspension layer than that of the l 15C,while agitating, after which it was distilled for l comparativesubstance.

Table 1 Blank Invention Comparison Dodecylbenzyl Dodecylbenzyl Samplenil A B isothiuronium pyridinum Surfactant chloride chloridePrecipitation Speed 1.24 4.19 4.53 1.17 1.72 (cm/min.)

hour at this temperature level to extract 7.6 kg. of acetic acid fromthe reaction system.

b. Test in aqueous solution of Amaranth red 100 cc of 0.01 percentsolution of Amaranth red was Subsequently, 20 kg. of 1,2-dichloroethanewas poured in each of five beakers of 200 cc capacity, into added to5.97 kg. of distilled residue and sufficiently agitated, and then 0.35kg. of calcium oxide was added to the distilled residue to neutralizethe same, thereafwhich each of the cationic surfactants A and Baccording to the present invention and the comparative substances shownin Table 1 above was added in an amount of 0.01 percent with respect tothe total quantity of water. The flocculating state was observed Table 3MOLECULAR FLOCCULAT- RAW WEIGHT ING EFFECT OF POLY- OF lSOTHl- MATERlALFORMALDEHYDE CATALYST SOLVENT REAC- REAC- CONDEN- URONIUM TION TlON SATESALT WITH TEMP. TIME RESPECT TO caolin SUSPENSION (C) (hrs) (cm/min)sulfuric 1,2- meta-xylene formaldehyde acid dichloro 80 5 l 140 4.28

ethane Z-methyl pnu hthalene f rm ldehyde aluminum acetic 1 l5 6 I7404.51

chloride acid 2,6- psulfuric acetic dimethyl formaldehyde acid acid l 5l480 4.36 naphthalene 'l-hutyl pnapthalene formaldehyde sulfuric aceticl 15 6 I030 4.09

acid acid t ir lin psulfuric acetic formaldehyde acid acid 1 l5 4 9804.2l meta-xylene formalin sulfuric l()() 7 3 l 8 3.51

acid metaxylene pp-toluene l.2-dich formaldeh de sulfonate loroethane 806 940 4.32 meta-xylene psulfuric acetic formaldehyde aCid acid l l5 l02730 4.86

2,6-dimethyl naphthalene No polycondensation conducted l.3l (forcomparison) NOTE:

The tests for the flocculating effect were conducted in the same manneras in Example l above. in which the polycondensate was chlorinated inthe same manner as in Example 1, and then connected into theisothiurnnium salt. The quantitative relationship among raw materialformaldehyde, catalyst. and solvent is substantially the same as inExample 1.

among these samples along with a blank solution containing no suchsurfactant. The results are shown in the following Table 2 in terms ofresidual chromaticity in the supernatant liquid, from which it will berecognized that the cationic surfactant according to the presentinvention possesses a remarkable effectv method which comprises thesteps of:

a. subjecting xylene to polycondensation by reacting the xylene withparaformaldehyde in the presence of a catalyst selected from the groupconsisting of sulfuric acid, aluminum chloride, para-toluene sulfonicacid, benzene sulfonic acid, zinc chloride and Table 2 Blank InventionComparison Dodecylbenzyl Dodecylhenzyl Sample Nil A B isothiuroniumpyridinum Surfactant chloride chloride Residual chromaticity 100 GT9 04698 99 (ppm) EXAMPLE 2 perchloric acid to produce a polycondensate of theVarious kinds of aromatic hydrocarbon compounds containing therein sidechains having active hydrogen at its (Jr-position and those compoundscontaining therein alicyclic structure were subjected topolycondensation under the reaction conditions as shown in Table 3below.

The polycondensates thus produced were further subjected to reactionsfor chlorination and subsequent xylene having a mean molecular weight offrom 200 to 3,000. b. introducing chlorine gas into said polycondensateunder irradiation of ultraviolet light to substitute chlorine for theactive hydrogen of the side chains of the xylene, while refluxing in asolvent selected from the group consisting of dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, perchloroethylene,chlorobenzene, benzene, nitrobenzene and benzonitrile, and

subjecting the resultant chlorinated polycondensate to treatment withthiourea to cause the thioruea to react with the chlorine introducedinto the polycondensate and thus render the chlorinated polycondensatewater-soluble.

2. The water-soluble cationic surfactant according to claim 1, whereinthe xylene is metaxylene.

1. A WATER-SOLUBLE CATIONIC SURFACTANT PRODUCED BY A METHOD WHICHCOMPRISES THE STEPS OF: A. SUBJECTING XYLENE TO POLYCONDENSATION BYREACTING THE XYLENE WITH PARAFORMALDEHYDE IN THE PRESENCE OF A CATALYSTSELECTED FROM THE GROUP CONSISTING OF SULFURIC ACID, ALUMINUM CHLORIDE,PARA-TOLUENE SULFONIC ACID, BENZENE SULFONIC ACID ZINC CHLORIDE ANDPERCHLORIC ACID TO PRODUCE A POLYCONDENSATE OF THE XYLENE HAVING A MEANMOLECULAR WEIGHT OF FROM 200 TO 3,000. B. INTRODUCING CHLORINE GAS INTOSAID POLYCONDENSATE UNDER IRRADIATION OF ULTRAVIOLET LIGHT TO SUBSTITUTECHLORINE FOR THE ACTIVE HYDROGEN OF THE SIDE CHAINS OF THE XYLENE, WHILEREFLUXING IN A SOLVENT SELECTED FROM THE GROUP CONSISTING OFDICHLOROMETHANE, CHLOROFORM, CARBON TETRACHLORIDE, 1,2-DICHLOROETHANE,PERCHLOROETHYLENE, CHLOROBENZENE, BENZENE, NITROBENZENE AN BENZONITRILE,AND C. SUBJECTING THE RESULTANT CHLORINATED POLYCONDENSATE TO TREATMENTWITH THIOUREA TO CAUSE THE THIORUEA TO REACT WITH THE CHLORINEINTRODUCED INTO THE POLYCONDENSATE AND THUS RENDER THE CHLORINATEDPOLYCONDENSATE WATER-SOLUBLE.
 2. The water-soluble cationic surfactantaccording to claim 1, wherein the xylene is metaxylene.